Alkyl hydroxy aromatic compounds



Patented Nov. 7, 1939 UNITED STATES PATENT OFFICE 2,178,571 ALKYL HYDBOXY ABOMATIC COMPOUNDS Lawrence H. Flatt,

No Drawing.

This invention relates to National Aniline New York, N. L,

Serial No. 737.777.

Hamburg, N. Y., assignor to 8;,Ohemical Company, Inc., a corporation of New York Original application July 31.

Divided and this application July 30, 1936, Serial No. 93,519

29 Claims.

mixtures of alkyl h droxy aromatic compounds and to methods of producing them. It tures of alkyl hydroxy the benzene series.

It is an object of relates particularly to mixaromatic compounds of the invention to provide mixtures of alkyl hydroxy aromatic compounds which may be manufactured in a simple and economical manner from easily available starting materials.

A further object of the a commercially feasible process for alkyl hydroxy aromatic comture of mixtures of pounds.

Other obvious, and

invention is to provide the manufacobiects of the invention will in part be will in part appear herelnaiter.

It has been found in accordance with the present invention that mixtures of alkyl hydroxy aromatic compounds obtainable by processes comp si g halogenation preferably consist ng of petroleum distillates, predominantly of saturated aliphatic, hydrocarbon compounds, condensation of the resulting halogenated with nuclear hydroxy aromatic fractions, ther eof products (or selected compounds, followed by rearrangement, if necessary, have considerable value for various purposes.

Thus, it has been found that by chlorinating a petroleum distillate, such as rolatum, and the like, and

condensing the chlorination product with a nuclear hydroxy aromat c compound, and particularly with a nuclear hydroxy aromatic compound (such as, for example, acid, chlorophenol,

oi the benzene series phenol, a cresol, cresylic salicylic acid, and the like),

compounds are obtained which may be employed with advantage as intermediates for the producton of su1fonation products which are valuable wetting, detergent, emulsifying,

to their use as the manufacture of the sulfonated the mixtures of alkyl hydroxy aroagents. In addition products in compounds,

and the like, intermediate matic compounds of the present invention may themselves be employed as pie, in the form of solutions detergents, for examof alcohol-water mixtures contain ng caustic alkali. Further, they may be employed asiticides, or vermicides', as junction with emulsifying as insecticides, germicides, parwetting agents in conagenis; as assistants n emulslfication; as solvents; as intermediates for the production of resins of all kinds in which phenols are reacted with resin-forming ingredients of various types; as pl asticizers for resinous products, cellulose plastics, and other synthetic or natural plastics; and as production of azo dyestuffs,

intermediates for the -for example, azo dyelrerosene. liquid petstuffs soluble in organic solvents, and/or useful for the dyeing of cellulose ethers and esters, etc.

As is well known in the art, petroleum distillates are mainly mixtures of aliphatic hydrocarbons including both saturated acyclic aliphatic hydrocarbons containing straight or branched carbon chains and cyclic aliphatic hydrocarbons as well as some unsaturated aliphatic hydrocarbons, depending upon the petroleum and the method of distillation, and/or purification. The petroleum distillates employed in the preparation of the present invention, however, preferably consist predominantly of saturated acyclic aliphatic hydrocarbons. When 7 are halogenated in the preparation of the products of the present invention, mixtures ofvarious halogenated derivatives of the said aliphatic hydrocarbons are produced (which are generically referred to herein ,as "alkyl halides"), and the said mixtures of the alkyl halides, when condensed with the hydroxy aromatic compounds, produce mixtures of alkyl hydroxy aromatic compounds of the type AHR, in whichTA represents an aromatic nucleus which may contain substituents, H represents a nuclear hydroxy group, and R represents a nuclear alkyl group containing a relatively large number of carbon atoms, the alkyl groups represented by R. corresponding with allphatic hydrocarbons of the petroleum distillate from which they are produced. (The term nu clear as employed herein with reference to a radical means that the radical is linked directly to a carbon atom of an aromatic nucleus represented by A. It appears that when a petrothe petroleum dlstillates into different positions in hydrocarbon molecules of the same structure; so that upon condensing a mixture of said alkyl halides with a. nuclear hydroxy aromatic compound, even though the initlal aliphatic hydrocarbon is the same, a mixture of nuclear alkyl hydroxy aromatic compounds of varied structure with respect to the alkyl groups in the compounds is produced. Accordingly, the compositions of the present invention are mixtures of alkyl hydroxy aromatic compounds represented by R have varied structures. It has been found that the mixtures of alkyl hydroxy aromatic compounds of this type are superior to a single alkyl hydroxy aromatic compound for many purposes when employed in equivalent amounts.

It will be evident the present invention has the additional important advantage that it provides a relatively simple and direct method of producing products having valuable properties from raw material which is readily available in large quantities, thereby making feasible the economical production of such products on a commercial scale.

In general, mixtures of alkyl hydroxy aromatic compounds of the said type AHR which are obtained from petroleum distillates consisting predominantly of saturated aliphatic hydrocarbon compounds, boiling at temperatures falling within the range of 215 C. at atmospheric pressure and 380 C. at 50 mm. pressure (and which in general contain not less than 12, and not more than 35, carbon atoms in the alkyl group represented by R) are of value, for the various purposes set out above, and, particularly, as intermediate products for the preparation of mixtures of sulionated products possessing superior detergent, and/or emulsifying action. However, compositions comprising mix tures of alkyl hydroxy aromatic compounds prepared from petroleum distillates containing predominantly saturated aliphatic hydrocarbons containing mainly 12 to 23, or still better 14 to 19 carbon atoms per molecule are of particular interest in accordance with the present invention. Thus, the compositions comprising mixtures oi alkyl hydroxy aromatic compounds which are obtained from petroleum distillates having boiling points within the range of about 215 C. at atmospheric pressure to about 260 C. at 50 mm. pressure (which corresponds approximately with 370" C. at atmospheric pressure),

believed contain about 12 to atoms in the alkyl groups represented by R, and especially those derived from petroleum distillates having boiling points within the range of about 235 C. at atmospheric pressure to about 215 C. at 50 mm. pressure (which corresponds approximately with 320 C. at atmospheric pressure), and which it is believed contain for the most part 14 to 19 carbon atoms in the alkyl groups represented by R, are

those with which the present invention is par- I ticularly concerned. Preferably, the petroleum distillates subjected to halogenation in the preparation of the products of the present inven tion should comprise, as the predominant fraction thereof, material boiling within the above noted preferred range of about 235 C. at atmospheric pressure to about 215 C. at 50 mm. pressure.

The aromatic nucleus represented by A in the foregoing formula may be derived from a carbocyclic or a heterocyclic mono-nuclear or polynuclear aromatic compound. It may be free from further substituents, or it may contain one or more additional atoms or groups attached to the carbon or other atoms of the nucleus, such as, for example, one or more additional hydroxyl radicals besides that represented by H in the foregoing formula; one or more additional alkyl groups which may be the same or different; and one or more of the atoms or radicals Cl, Br, I, F, COOH, COORa, CORE, ORa, and Ra (in which R5 represents any alkyl, aryl, hydroaryl, alkaryl, aralkyl, cycloalkyl, or heterocyclic radical, which groups or radicals may be further substituted or not and, if more than one is present, may be the same or different).

As pointed out above, those products are of particular importance in which the aromatic nucleus represented by A is the residue of a hydroxy aromatic compound of the benzene series, such as, for example, phenol, ortho-, meta-, or para-cresol, cresylic acid, salicylic acid, chlorophenol, and the like.

In preparing the compositions comprising mixtures of alkyl hydroxy aromatic compounds of the present in accordance with by weight, the

Example 1 Part 1.Chlorine is passed into 328 parts of a kerosene (a Pennsylvania petroleum distillate) which boils from 235 to 240 while maintaining the temperature at 50. To facilitate the reaction, the reaction mixture, which is contained in a glass reaction vessel, is subjected to parts, the introduction of chlorine is discontinued and the agitation continued for about an additional fifteen minutes. The reaction mixture is subjected to fractional distillation, and a middle fraction is collected between and 175 at 34 mm. pressure of mercury. It

comprises mainly monochlorinated hydro-.

carbons.

Part 2.150 parts of the resulting chlorinated hydrocarbon product, 150 parts of phenol and 130 parts of anhydrous zinc chloride are agitated while being heated at in a vessel provided with a reflux condenser. After about five hours, the heating is discontinued, the mixture is allowed to cool, is washed with dilute hydrochloric acid (100 parts of 10 per cent H01), and is then distilled at 4 mm. pressure. The por tion of the product boiling from 140 to 250 at 4 mm. pressure is separately collected, about three-fourths of which boils between and 220. The product is comprised mainly of a mix ture 01 alkyl phenols which may be represented by the general formula:

in which R is a primary, secondary or tertiary alkyl group, which for the most part is probably in the para-position to the hydroxyl group, the average number of carbon atoms in the groups represented by R. probably being about it. r

- Example 2 Chlorine is passed into 400 parts of a kerosene boiling from about 195 to about 300 (and boiling for the most part from about 225 to 275), having a specific gravity of 0.799 at 24', containing about 5.6 per cent 01 unsaturated hydrocarbons, and having a probable carbon content ranging from 11 to 18 carbon atoms and a probable average content of about 18.4 carbon atoms, at 50 in difl'used light until there is an increase or weight 0! 111 parts, 2.parts or which is due to dissolved hydrogen chloride. The resulting product comprises unchlorinated hydrocarbon in admixture with mono-, di-, and poly-chlorinated hydrocarbons, the average chlorine content oi the mixture being equivalent to about one and one-half atoms of chlorine per molecule of hydrocarbon having the stated carbon content. 150 parts oithis chlorinated mixture is slowly added to an agitated mixture of 200 parts, phenol and 5 parts anhydrous zinc chloride at 75. and the temperature is maintained at 75 for about 30 minutes after all the chlorinated mixture has been added. The temperature 0! the mixture is then raised and maintained at 135 ior 2.5 hours. 5 parts oi! zincdust is then added, and after one hour another 5 parts of zinc dustis added, the temperature being maintained during this addition, and for about 3 hours afterward, at 135. The reaction mixture is cooled, treated with water, and the oil is separated from the water and residual zinc dust and tractionally distilled. The fraction boiling irom 140 to 250 at 4 mm. pres sure is separately collected; It comprises a mixture of saturated and unsaturated alkyl phenols and chloralkyl phenols, the alkyl groups containing a probable average content of about 13 carbon atoms.

Example 3 Bart 1.-A crude chlorinated kerosene is prepared by chlorinating at.5,0, in a lead-lined vessel, a kerosene of the type employed in Example 2,

until the reaction mixture reaches a specific gravity of 0.91. I

Part 2.l50 parts of the product of Part 1 of this example are reacted with 200 parts oi phenol as described in Example 2. The crude product is washed with water and distilled in vacuo. The fraction distilling from 140 to 240 at 3 mm. pressure is separately collected. It comprises a mixture of alkyl phenols in which the alkyl groups have a probable average content of 13 carbon atoms. The alkyl groups are probably for the main part saturated alkyl hydrocarbon groups.

Example 4 Chlorine is passed into 300 parts of a purified drogen chloride present.

crease in weight for the formation of the monochloride.) 200 parts of the resulting chlorinated white 011, 200 parts of phenol and 35 parts of anhydrous zinc chloride are heated and refluxed at 170 for about 5 hours in the manner described in Example 1, Part 2. The oily product is decanted from the zinc chloride and is lractlonally distilled in vacuo. The distillate boiling from 240 to 300" at 3 mm.- pressure is separately collected. It comprises a mixture of alkyl phenols in which the alkyl groups have a probable average content of about 23 carbon atoms.

Example 5 chlorlde, the introduction of chlorine is discontinued but the agitation is continued for an additional fifteen minutes. 200 parts of the resulting chlorinated kerosene, parts of phenol and 35 parts of anhydrous zinc chloride are refluxed for 5 hours. zinc chloride and is iractionally distilled in vacuo. The distillate boiling from 190' to 275 C. at 4 mm. pressure is separately collected. It is comprised chiefly of a mixture of alkyl phenols wherein the average number of carbon atoms in the alkyl groups is probably about 1'7.

Example 6 200 parts oi! the crude, undistilled, chlorinated hydrocarbon product of Example 3, Part 1, 125 parts of phenol and 25 parts of zinc dust are heated under refluxing and agitation at 170 for about 4 hours. The oily product is decanted from the zinc residues and lractionally distilled in vacuo. The portion of the distillate boiling from 160 to 250 at 4 mm. pressure is separately collected. It is similar to the product resulting from the process of Example 3.

Example 7 150 parts of the chlorinated hydrocarbon prodnot prepared in Example 3, Part 1, 150 parts of phenol, parts of anhydrous zinc chloride and 10 parts of tetrachlorethane are heated under refluxing and agitation at to for about 3 hours, an additional 10 parts of tetrachlor ethane being added after the reaction has proceeded for about 2 hours. The oily reaction mixture is decanted from the zinc chloride, washed with 10 per cent hydrochloric acid and fractionally distilled in vacuo. The portion of the distillate boiling from to 240 at 10 mm. pressure is separately collected. It is similar to the product resulting from the process of Example 3.

Example 8 Chlorine is passed into 300 parts of kerosene (boiling from about 210 to about 255, and for the most part from about 220 to 240) at 5 to 15' until there is a gain in weight of 58 parts, exclusive of the small amount of dissolved by- 150 parts of the resulting chlorinated kerosene, 70 parts of commercial The oily product is decanted from the cresylic acid and 25 parts of anhydrous zinc chloride are agitated vigorously and heated at 135 for 45 minutes. After cooling, the liquid is decanted from the solid material and washed with about 100 parts of 10 per cent hydrochloric acid. The washed oil is vacuum distilled, and the fraction of the distillate boiling between 190 and 240 at 8 mm. pressure is separately collected. It is an amber to white liquid and is comprised chiefly of a mixture 01 alkyl cresols corresponding with the general formula:

in which R" is a primary, secondary or tertiary alkyl group and in which the alkyl groups repre-- sented by R" have a probable average content of 12 to 15 carbon atoms.

Example 9 in which R' is a primary. secondary or tertiary alkyl group, probably mostly in ortho-position to the hydroxyl group. the average number or carbon atoms in the alkyl groups represented' by.

R'" probably being about 13.

Example 10 100 parts of m-cresol are employed instead of the p-cresol 01' Example 9. The portion 01' the resulting product boiling from 185 to 205 at 6 mm. pressure is separately collected. It comprises mainly a mixture of alkyl m-cresols which may be represented by the general formula:

in which R' is a primary, secondary or tertiary alkyl group, the said alkyl groups having a probable average content of about 13 carbon atoms.

Example 11 150 parts of the crude, undistilled chloride of Example 1, Part 1, 20 parts of anhydrous zinc chloride and 100 parts of o-cresol are heated to 135 for 10 hours, the resulting oil decanted oil and distilled. The portion of the resulting prod uct boiling from 160 to 250 at 4 mm. pressure is separately collected. It comprises mainly a mixture of alkyl o-cresols which may be represented by the general formula:

in which R is a primary, secondary or tertiary alkyl group, the said alkyl groups having a probable average content of about 14 carbon atoms.

Example 12 Chlorine is passed into 300 parts of kerosene (boiling from about 210 to 255 and for the most part from about 220' to 240). at 5 to 15 until there is a gain in weight 01' 58 parts exclusive of the dissolved hydrogen chloride. 150 parts 01' the chlorinated kerosene, 80 parts 01' o-chlorophenol and parts of anhydrous zinc chloride are agitated vigorously and heated at 135 for minutes. The liquid is decanted from the solid and washed once with about 100 parts of 10 per cent hydrochloric acid. The oil is vacuum distilled. The fraction boiling between 180 and 250 at 0 mm. pressure is collected separately. It is a brown to white liquid comprised chiefly of a mixture of allwl o-chlorophenols corresponding with the general i'ormula:

Cl n in which R" has the meaning above given in Example 8.

Example 13 Chlorine is passed into 300 parts oi kerosene (boiling from about 210 to 255 and for the most part from about 220 to 240) at 5 to 15 until there is a gain in weight of 58 grams exclusive of the dissolved hydrogen chloride. 150 parts of the chlorinated kerosene, 90 parts of salicylic acid and parts of anhydrous zinc chloride are agitated vigorously and heated at 140 to 150 for 4 ,hours. When the reaction mixture cools to 80", 100 parts of water are added, and then about 70 parts of ether. The zinc chloride is removed by washing several times with water. The ether solution is extracted with sodium carbonate solution. The sodium carbonate solution is boiled to,

remove any dissolved ether, acidified with hydrochloric acid and heated. The excess salicylic acid dissolves and leaves the alkyl salicylic acid as an oil. The crude alkylated salicylic acid when cold is a brown, gummy solid. It forms a good detergent with alkali.

Example 14 800 parts of the chlorinated hydrocarbon product employed in Example 1, Part 2, 400 parts 'of crude pyrogallol and 50 parts of zinc chloride are agitated and heated in a container at 160 for 17 hours. The oly product is decanted from the hard residue which has formed, and distilled in vacuo. The portion of the distillate boiling from 220 to 260 at 3 mm. pressure is separately collected. It comprises mainly a mixture 01 alkyl pyrogallols which may be represented by the general iormula:

in which R is a primary, secondary or tertiary alkyl group, the said alkyl groups having an average content of probably about 14 carbon atoms.

Example 15 necessary, by cooling the reaction mixture. After the reaction has moderated, the reaction mass is maintained at a temperature of tor 3 hours, the mixture is poured onto ice, acidified with hydrochloric acid, and the oil which separates is washed with dilute caustic soda solution and distilled. The fraction which distllls over at 200 to 230 at 3 mm. pressure is separately collected. The product thus obtained comprises an alkylated hydroxy-quinoline having the following general formula:

wherein Rf is a primary, secondary or tertiary alkyl group which probably contains an average or 13 to 15 carbon atoms.

Example 16' mixture of alkyl p-hydroxydiphenyls in which the average content of the alkyl group about 13,carbon atoms.

Example 17 Chlorine is passed into 300 parts of kerosene (a South Texas petroleum distillate) boiling from 185 to 281,havinga specific gravity of 0.823 at 24, an average composition probably corresponding to ClzsI-Im, and containing 1 per cent of unsaturated hydrocarbon. The kerosene which is contained in a glass vessel is maintained at a temperature of about 25 to 40 and subjected to diflused daylight for 2 hours, and then is maintained at 50 while subjected to actinic light from a mercury lamp tor an hour or until the reaction is probably mixture has increased about 59 parts in weight (which corresponds approximately to monochlorination). A mixture of 300 parts of this chlorlnated kerosene, 150 parts of phenol and 25 parts oi anhydrous zinc chloride is heated, with agitation, to 135 for 10 hours; the reaction mixture is cooled and then washed with water, and the oily residue is distilled in vacuo. The fraction distllling from 150" to 250 at 4 mm, pressure is separately collected. It comprises an alkyl phenol mixture in which the alkyl groups have a probable average content of about 12 to 13 carbon atoms.

Example 18 420 parts of bromine dissolved in 1600 parts oi carbon tetrachloride are slowly added in small portions at a time to 500 parts of kerosene of the type employed in Example 2 contained in a glass vessel, at ordinary temperature in the presence of actinic light from a mercury lamp. The resuiting crude product, after distilling oil the carbon tetrachloride, comprises a mixture of brominated hydrocrabons. 108 parts of this crude prodnot is mixed with 75 parts of phenol and 10 parts of anhydrous zinc chloride, and the mixture is heated at 135 for 4 hours. The resulting mass is cooled, washed with water, and distilled under reducedpressure, The fraction distilling between 140 and 205 at 4 mm. pressure is separately collected. phenols in which the alkyl groups have a probable average content of about 13 carbon atoms.

Example 19 Part 1.--Chlorine is passed into a kerosene (a purified Pennsylvania petroleum distillate (boiling from 245 to 315, and of which 90 per cent distills between 260 and 305, and having a specific gravity of 0.815, contained in a closed, lead-lined vessel which is equipped with a vent for hydrogen chloride produced by the chlorination. The chlorination is carried out in the dark, but to facilitate the chlorination the kerosene initially contains about 0.45 part of iodine per 1000 parts of kerosene. The temperature of the reaction mass is preferably maintained at about 45 to 50. The introduction of chloride is continued until the weight of the mass increases to an extent correspond ng substantially with per cent of the theoretical amount for the formation of the monochloride. The specific gravity of the reaction mixture reaches about 0.915.

Part 2.560 parts of the resulting mixture of chlorinated hydrocarbons, 350 parts of phenol and 28 parts of granular anhydrous zinc chloride are agitated at room temperature for about 3 hours and then heated, with agitation, at about for about 5 hours, The resulting reaction mass is cooled and added to about 600 parts of water, the mixture is heated to 70 with agitation, allowed to settle, and the upper, oil layer is separated and washed with hot water to remove zinc chloride and residual phenol. The washed oil is then treated with a small amount of alkali (7 parts of a 50 per cent solution oi sodium hydroxide) and distilled in vacuo (e. g., 4 mm. pressure) in a, still equipped with a fractionating column. Fractions boiling between about and 230 at 4 mm. pressure are collected as separate products or as one product,

It will be realized by those skilled in the art that changes may be made in the products, and in the processes of preparing and, using them, hereinbefore described, without departing from the scope of the invention.

It comprises a mixture of alkyl' compounds Thus, the mixed alkyl hydroxy aromatic compounds of the said type AHR may be prepared in variousfways from various fractions of petroleum distillatbs, preferably consisting predominantly of saturated aliphatic hydrocarbon compounds. The most important sources of rawmaterial i'or the preparation of the alkyl hydroxy aromatic are the kerosene fractions derived from parailinic and/or asphaltic petroleums as, for example, those obtained from Pennsylvania, Texas, or Oklahoma petroleums, those obtained from Pennsylvania petroleum being especially preferred.

As will be evident from the foregoing examples. the invention includes products prepared from various fractions of petroleum distillates and boiling over a wide or narrow range of temperatures. For general use, the products are prepared from kerosene fractions of wide boiling range. For individual purposes, preferred products are obtained by employing as initial material a kerosene fraction of narrow boiling range. The use of fractions of petroleum distillates of relatively small boiling range has the advantage of facilitating the separation by distillation of the free phenol, free hydrocarbon and alkyl phenol irom each other, or of the halogenated hydrocarbons from residual unhalogenated hydrocarbons. As hereinabove pointed out, for most purposes, and particularly as intermediate products for the preparation of sulfonated products useful as detergents, products are preferred which are derived from petroleum distillates consisting predominantly of saturated aliphatic hydrocarbons having a carbon content of 12 or more carbon atoms, and particularly 12 to 23 carbon atoms, and boiling for the most part between about 215 C. at atmospheric pressure and about 260 C. at 50 mm. pressure.

The chlorination of the petroleum hydrocarbon may be carried out by any well-known process. The approximate extent of chlorination may be determined by the increase in the weight of the hydrocarbon material chlorinated, or by the increase of the specific gravity of the mixture. Various chlorination temperatures may be employed, for example, temperatures within the range 0 to 70 0., and preferably in the neighborhood 0150 C. If desired,or necessary, the chlorination may be carried out with the aid of chlorine carriers, catalysts, or adjuvants, as, for example, phosphorus trichloride, iodine, sunlight, etc.

In general, the extent of chlorination of the petroleum hydrocarbon may be regulated by a weight increase corresponding to a product containing a ratio of about 0.25 to 2.5 atoms of chlorine per molecule 01 hydrocarbon, about 1.1 to 1.5 atoms being preferred, but it will be understood that other ratios may be used. Ordinarily, the greater the amount or extent of chlorination, the greater is the boiling residues obtained. In general, the monochloride boils about 15 to 20 C. higher than the petroleum distillate from which it is derived. I1 desired, the chlorinated products may be fractionally distilled so as to obtain a further selection and restriction of alkyl compounds having a selected content of chlorine atoms. Instead of chlorine, other halogens may also be employed in effecting halogenation; e. g., bromine, etc.

The condensation of the halogenated hyrocarbon with the hydroxy aromatic compound may be carried out with the aid of other condensing agents than zinc chloride; as, for example, metals (such as zinc or iron), other metal halides (such amount of high agent since, on thewhole, it gives a more uniform product and better yield.

The proportionof mixed alkyl halides with respect to the hydroxy aromatic compound employed in the preparation of the .alkylated hydroxy aromatic compounds may be varied. Preferably, the proportion of mixed halogenated hydrocarbons employed with respect to the hydroxy aromatic compound is such that only one alkyl radical of the type represented by R in the foregoing formula is contained in the resulting alkyl hydroxy aromatic compounds. Thus, at least 1.75 mole of hydroxy aromatic compound per moi of mixed halogenated hydrocarbons is preferably employed in the condensation. A molar ratio as low as 1 to 1 may be employed, but the yield of the resulting alkyl hydroxy aromatic compounds containing one long alkyl group will be less. Further, the amount of condensing agent employed may vary over a wide range. For example, in using anhydrous zinc chloride as the condensing agent, in some cases, as low as 1 per cent and in others about 5 to 10 percent or more by weight of anhydrous zinc chloride, based upon the amount of halogenated petroleum hydrocarbon, may be employed. The condensation reaction may be carried out at any suitable tem- U perature. However, when a zinc chloride condensing agent is employed, temperatures between 60 and about 180 C. are ordinarily preferred.

The duration of the condensation treatment may also be varied, the particular period of condensation being dependent to someextent upon the condensation temperature employed as well as the particular condensing agent used and the nature of the desired product. The condensation is ordinary complete in about 1 hour at refluxing temperature (approximately 170 C. for phenol), or in about 3 to 6 hours at about 135 (2., when employing a metal halide condensing agent. With anhydrous zinc chloride as the condensing agent, the period of heating may be extended to 16 hours or more without seriously harming the quality or substantially decreasing the yield of alkyl hydroxy aromatic compounds.

The mixtures of alkyl hydroxy aromatic compounds may also be prepared in other ways. Thus, the mixed alkyl halides resulting from halogenation of the selected fraction of petroleum distillate may be reacted with an alkali metal phenolate or other metal compound of the hydroxy aromatic compound desired to be alkylated, to form a mixture of alkyl ethers of said hydroxy aromatic compound, and the resulting ether mixture may be subjected to rearranging treatment according to processes similar to those used for rearrangement of known alkyl ethers of phenols, to convert the said ethers to the corresponding alkyl hydroxy aromatic compounds.

Mixtures of hydroxy aromatic compounds of the said type AH may be employed as reacting ingredients, if desired; as, for example, naturally occurring mixtures such as commercial cresylic acid, or artificially prepared mixtures of two or more of said hydroxy aromatic compounds.

The alkyl hydroxy aromatic compounds may be purified by fractional or steam distillation, or by other suitable processes.

Since certain changes may be made in the above processes and products without departing from the scope of the present invention it is intended that all matter contained in the above decontinuation-impart of my applications Serial Nos. 691,081 and69l,082 filed September 26, 1933.

I claim:

1. A mixture of alkyl hydroxy aromatic compounds of the type AHR which mixture is obtainable by the halogenation of a petroleum distillate consisting predominantly of saturated aliphatic hydrocarbons, to form mixed alkyl halides, and conversion of a hydroxy aromatic compound of the type AH to a mixture of alkyl hydroxy aromatic compounds of the type AHR by a process including reaction thereof with resulting mixed alkyl halides; A representing an aromatic nucleus, H representing a nuclear hydroxyl group, and R representing an alkyl group containing at least 12 carbon atoms.

2. A mixture of alkyl hydroxy aromatic compounds oi. the type AHR which mixture is obtainable by the halogenation or a petroleum distillate consisting predominantly of saturated aliphatic hydrocarbons, to form mixed alkyl halides, and conversion of a hydroxy aromatic compound of the type AH to a mixture of alkyl hydroxy aromatic compounds or the type AHR by a process including reaction thereof with resulting mixed alkyl halides; A representing an aromatic nucleus, H representing a nuclear hydroxyl group, and R representing an alkyl group containing from 12 to 23 carbon atoms.

3. A mixture of alkyl hydroxy aromatic compounds of the type AHR which mixture is obtainable by the halogenation of a petroleum distillate consisting predominantly of saturated aliphatic hydrocarbons, to form mixed allavl halides, and conversion of a hydroxy aromatic compound of the type AH to a mixture or alkyl hydroxy aromatic compounds or the type AHR by a processincluding reaction thereof with the resulting mixed alkyl halides; A representing an aromatic nucleus, H representing a nuclear hydroxyl group, and R representing an alkyl group containing from 14 to 19 carbon atoms.

4. A mixture of alkyl hydroxy aromatic compounds of the type AHR which mixture is obtainable by the chlorination 01! a petroleum distillate boiling within the range about 215 C. at atmospheric pressure and about 380 C. at 50 mm. pressure, and consisting predominantly of saturated aliphatic hydrocarbons, to form mixed alkyl chlorides, and conversion of a hydroxy aromatic compound of the type AH to a mixture of alkyl hydroxy aromatic compounds of the type AHR by a process including reaction thereof with resulting mixed alkyl chlorides; A representing an aromatic nucleus of the benzene series, H representing a nuclear hydroxyl group, and R. representing an alkyl group.

5. A mixture of alkyl hydroxy aromatic compounds of the type AHR which mixture is obtainable by the chlorination of a petroleum distillate boiling within the range of about 215 C. at atmospheric pressure and about 260 C. at 50 mm. pressure, to form mixed alkyl chlorides, and conversion of a hydroxy aromatic compound of the type AH to a mixture of alkyl hydroxy aromatic compounds of the type AHR by a process including reaction thereof with resulting mixed alkyl chlorides; A representing an aromatic nucleus of the benzene series, H representing a nuclear hydroxyl group, and R representing an alkyl 10111).

alkyl chlorides;

6. A mixture oi alkyl hydroxy aromatic compounds of the type AHR which mixture is obtainable by the chlorination of a petroleum distillate boiling within the range of about 215 C. at atmospheric pressure and about 260 C. at 50 mm. pressure, to form mixed alkyl chlorides, and conversion of a hydroxy aromatic compound of the type AH to a mixture of alkyl hydroxy aromatic compounds of the type AHR by a process including reaction thereof with resulting mixed A representing an aromatic nucleus of the benzene series, H representing a nuclear hydroxyl group, and R representing an alkyl group; said mixture containing a plurality of compounds of the said type AHR in some of which the alkyl group represented by R is unsaturated and in others of which it is saturated.

7. A mixture of alkyl hydroxy aromatic compounds of the type AHR which mixture is obtainable by the chlorination of a petroleum distillate boiling within the range of about 215 C. at atmospheric pressure and about 260 C, at 50 mm. pressure, to form mixed alkyl chlorides, and conversion of a hydroxy aromatic compound of the type AH to a mixture of alkyl hydroxy aromatic compounds of the type AHR by a process including reaction thereof with resulting mixed allwl chlorides; A representing an aromatic nucleus of the benzene series, H representing a nuclear hydroxyl group, and R representing an alkyl group; said mixture containing a plurality of compounds of the said type AHR in some of which the alkyl group represented by R is a chloralkyl group.

8. A mixture of alkyl hydroxy aromatic com pounds of the type AHR which mixture is obtainable by the chlorination of a petroleum distillate boiling within the range of about 215 C. at atmospheric pressure and about 260 C. at 50 mm. pressure, to form mixed alkyl chlorides, and conversion of a hydroxy aromatic compound of the type AH to a mixture of alkyl hydroxy aromatic compounds of the type AHR by a process including reaction thereof with resulting mixed alkyl chlorides; A representing an aromatic nucleus of the benzene series, H representing a nuclear hydroxyl group, and R representing an alkyl group; said mixture containing a plurality of compounds of the said type AHR in some of which the alkyl group represented by R is unsaturated and in others of which it is saturated and in others of which it is a chloralkyl group.

9. A mixture of alkyl hydroxy aromatic compounds oi' the type AHR which mixture is obtainable by the chlorination of a Pennsylvania petroleum distillate boiling within the range about 235 C. at atmospheric pressure and about 215 C. at 50 mm. pressure, and consisting predominantly of saturated aliphatic hydrocarbons, to form mixed alkyl chlorides, and conversion of a hydroxy aromatic compound of the type AH to a mixture or alkyl hydroxy aromatic compounds of the type AHR by a process including reaction thereof with resulting mixed alkyl chlorides; A representing an aromatic nucleus or the benzene series, H representing a nuclear hydroxyl group, and R. representing an alkyl group.

10. A mixture of alkyl phenols of the type (R representing an alkyl hydrocarbon group conso a hydroxy aromatic compound taining at least 12 carbon atoms and derivable by chlorination oi a kerosene traction of petroleum distillate), said mixture containing a plurality of related alkyl phenols of said type which differ fronnpach other in the alkyl hydrocarbon group represented by R. i

11. A mixture 01' alkyl phenols that contains as a nuclear substituent a single alkyl group containing at least 12 carbon atoms and derivable by chlorination of a kerosenetraction of petroleum distillate and condensation of a mixture of resulting alkyl chlorides with a phenol of the benzene series, said alkyl phenol mixture containing a plurality of related alkyl phenols which difler from each other in the alkyl groups.

12. A mixture of monoalkyl monohydroxy benzenes that difler from each other in the alkyl groups, which alkyl groups correspond with the aliphatic hydrocarbons 01' a petroleum distillate boiling within the range about 215 C. at atmospheric pressure and about 260 C. at mm. pressure.

13. A process for the preparation of an alkyl hydroxy aromatic compound which comprises halogenating a petroleum distillate consisting predominantly of saturated aliphatic hydrocarbons containing at least 12 carbon atoms to form mixed alkyl halides, and condensing at least a portion oi the resulting mixed alkyl halides with of the type AH; A representing an aromatic nucleus and H representing a nuclear hydroxyl group.

14. A process for the preparation of an alkyl hydroxy aromatic compound which comprises halogenating a petroleum distillate consisting predominantly oi saturated aliphatic hydrocarbons containing from 12 to 35 carbon atoms per molecule, to form mixed alkyl halides, and condensing at least a portion or the resulting mixed alkyl halides with a hydroxy aromatic compound to form an alkyl hydroxy aromatic compound.

15. A process for the preparation of a mixture of alkyl hydroxy aromatic compounds which oomprises halogenating a petroleum distillate consisting predominantly of saturated aliphatic hydrocarbons containing from 12 to 35 carbon atoms per molecule, to form mixed alkyl halides. and condensing the resulting mixed alkyl halides with a hydroxy aromatic compound of the type AH; A representing an aromatic nucleus and H representing a nuclear hydroxyl group.

16. A process for the preparation of a mixture of alkyl hydroxy aromatic compounds of the henzene series which comprises halogenating a petroleum distillate consisting predominantly oi saturated aliphatic hydrocarbons containing from 12 to 35 carbon atoms per molecule, to form mixed alkyl halides, condensing at least a portion or the resulting mixed alkyl halides with a hydroxy aromatic compound oi the benzene series, to form a mixture of alkyl hydroxy aromatic compounds 01' the benzene series, and recovering a mixture or said alkyl hydroxy aromatic compounds.

17. A process for the preparation of a mixture of alkyl hydroxy aromatic compounds of the benzene series which comprises chlorinating a petro. leum distillate boiling for the most part within the range about 215 C. at atmospheric pressure and about 260 C. at 50 mm, pressure to form mixed alkyl chlorides, condensing at least a portion of the mixed alkyl chlorides with a hydroxy aromatic compound of the benzene series in the presence of zinc chloride to form a mixture or alkyl hydroxy aromatic compounds at the henzene series, and recovering a mixture of said alkyl hydroxy aromatic compounds.

18. A process for the preparation of a mixture alkyl phenols which comprises chlorinating a petroleum distillate boiling for the most part within the range about 235 C. at atmospheric pressure and about 215 C. at 50 mm. pressure and consisting predominantly of saturated aliphatic hydrocarbons, to form mixed alkyl chlorides, condensing at least a portion of the mixed alkyl chlorides with phenol in the presence of anhydrous zinc chloride to form a mixture of alkyl phenols, and recovering a mixture of said alkyl phenols.

19. A process for the preparation of a mixture of alkyl hydroxy aromatic compounds which oomprises chlorinating with the aid of light a petroleum distillate consisting predominantly of saturated aliphatic hydrocarbons containing at least 12 carbon atoms to form mixed alkyl chlorides, and condensing at least a portion of the resulting mixed alkyl chlorides with a hydroxy aromatic compound oi the type AH; A representing an aromatic nucleus and H representing a nuclear hydroxyl group.

20. A process for the preparation of a mixture of alkyl hydroxy aromatic compounds which comprises chlorinating a petroleum distillate boiling for the most part within the range about 215 C, at atmospheric pressure and about 260 C. at 50 mm. pressure, continuing the chlorination until the amount of combined chlorine in the resulting product corresponds with 1.1 to 1.5 atoms of combined chlorine per molecule oi petroleum hydrocarbon, and condensing at least a portion of the mixed alkyl chlorides with a hydroxy aromatic compound oi the benzene series with the aid of a metal halide condensing agent.

21. A process for the preparation of a mixture 04' alkyl hydroxy aromatic compounds, which comprises chlorinating with the aid of light a Pennsylvania petroleum distillate which for the most part boils between about 215 C. at atmospheric pressure and about 260 C. at 50 mm.

pressure, continuing the chlorination until the amount or combined chlorine in the resulting product corresponds with 1.1 to 1.15 atoms of combined chlorine per molecule of petroleum hydrocarbon, and condensing the resulting mixture of alkyl chlorides with a phenol of the benzene a series with the aid of zinc chloride as a condensing agent.

22. A mixture of monoalkyl monohydroxy benzenes that difler from each other in the alkyl groups, which alkyl groups correspond with the" aliphatic hydrocarbons of a kerosene fraction of Pennsylvania petroleum which boils from 235 to 240 C. at atmospheric pressure and are derivable by chlorination of such a kerosene.

23. A mixture of alkyl cresols that contain as a nuclear substituent a single higher alkyl group containing at least 12 carbon atoms and derivable by chlorination 01' a kerosene fraction of petroleum distillate and condensation of a mixture of resulting alkyl chlorides with a cresol, said alkyl cresol mixture containing a plurality oi related alkyl cresols which difler from each other in said higher alkyl groups.

24. A mixture of alkyl cresols that contain as a nuclear substituent a single higher alkyl group, said alkyl cresol mixture containing a plurality of related alkyl cresols wh'ch differ from each other in said higher alkyl groups, said alkyl cresol mixture being derivable by chlorination of a kerosene boiling from about 195 to about 300 C. and

ai'rasri boiling for the most part from 225 to 2'15 0.. at atmospheric pressure. and containing about 5.6 per cent of unsaturated hydrocarbons. and condensation of the mixture of resulting albl chlorides'with a cresoi.

25. A mixture of alkyl para-cresois that contain as a nuclear substituent a single higher allgvl group, said alkyl para-cresol mixture containing a plurality of related albl para-cresols which diiler from each other in said higher alkyl groups, said aikyl para-cresol mixture being derivable by chlorination of a kerosene boiling from about 195 to about 300 C. and boiling for the most part from 225' to 275 C., at atmospheric pressure, andcontaining about 5.6 per cent of unsaturated hydrocarbons, and condensation of the mixture 0! resulting alkyl chlorides with para-cresol.

26. A process for the preparation of a mixture of monoalkyl monohydroxy benzenes which comprises chlorinating a petroleum distillate boiling from 235 to 240 C. at atmospheric pressure. subjecting the reaction mixture to fractional distillation, collecting a middle iraction of the dis- -til1ate comprising mainly monochlorinated hydrocarbons, and condensing said fraction of chlorinated hydrocarbons with phenol with the aid of zinc chloride as a condensing agent.

2'2. A process for the preparation oi a mixture of alkyl hydroxy aromatic compounds which comprises chlorinating a kerosene boiling Irom CERTIFICATE or commoner.

Patent 110. 2,173,571.

It is hereby certified that error appears 1 the above numbered patent requiring correc o insertaparenthesis; page 1;, secondoelend column, line 51 atter'a.

\um, line 71, Example 11;, for "e17" read oily; page 5, second colimn: for distillate (boiling! read distillate) boil ng,

read chlorine; pag B,

.5; and that the said'Lettere Patent therein tint the same may conform to 56, Example 19-, V 1 .7, same example, ror chloride" line I 7, claim 21, "or" 1.15"' read 1 should be read pith this correction LAWREICE H. FIE'IT.

195' to 300 C. and boiling for the most part irom 225' to 275 0., and containing about 5.8 per cent of unsaturated hydrocarbona'to produce a chlorination product containing mono-. diand poly-chlorinated hydrocarbons, condensing the resulting chlorination product with a phenol of the benzene series in the presence at zinc chloride as a condensing agent to form a mixture oi alkyl phenols and recovering a mixture of said alkyi phenols.

28. A process for the preparation of a mixture of alkyl cresols which comprises chlorinating a petroleum distillate consisting predominantly of saturated aliphatic hydrocarbons containing at least 12 carbon atoms to form mixed alkyl chlorides, condensing at least a portion of the resulting mixed alkyl chlorides with a cresol, and re covering a mixture of said alkyl cresols.

29. A process for the preparation of a mixture of higher alkyl cresols which comprises chlorinating a kerosene boiling from 195 to 300 C. and boiling for the most part from 225' to 2'15 0., and containing about 5.6 per cent of unsaturated hydrocarbons. to produce a chlorination product containing mono-, diand poly-chlorinated hydrocarbons. condensing the resulting chlorination product with a cresol in the presence of nnc chloride as a condensing agent. to form a mixture of higher aikyi cresols. and recovering a mixture Said h ther alkyl c'resols.

' LAWRENCE H. mm.

ilovemher 7, 1939.

in the printed specification tionas iollower Page 1, secline line

second column,

the record or the case in the Patent Office.

Signed and sealed this 6th Seal day of February,

Henry Van Lrsdale, acting Goaniasipneref ratents ai'rasri boiling for the most part from 225 to 2'15 0.. at atmospheric pressure. and containing about 5.6 per cent of unsaturated hydrocarbons. and condensation of the mixture of resulting albl chlorides'with a cresoi.

25. A mixture of alkyl para-cresois that contain as a nuclear substituent a single higher allgvl group, said alkyl para-cresol mixture containing a plurality of related albl para-cresols which diiler from each other in said higher alkyl groups, said aikyl para-cresol mixture being derivable by chlorination of a kerosene boiling from about 195 to about 300 C. and boiling for the most part from 225' to 275 C., at atmospheric pressure, andcontaining about 5.6 per cent of unsaturated hydrocarbons, and condensation of the mixture 0! resulting alkyl chlorides with para-cresol.

26. A process for the preparation of a mixture of monoalkyl monohydroxy benzenes which comprises chlorinating a petroleum distillate boiling from 235 to 240 C. at atmospheric pressure. subjecting the reaction mixture to fractional distillation, collecting a middle iraction of the dis- -til1ate comprising mainly monochlorinated hydrocarbons, and condensing said fraction of chlorinated hydrocarbons with phenol with the aid of zinc chloride as a condensing agent.

2'2. A process for the preparation oi a mixture of alkyl hydroxy aromatic compounds which comprises chlorinating a kerosene boiling Irom CERTIFICATE or commoner.

Patent 110. 2,173,571.

It is hereby certified that error appears 1 the above numbered patent requiring correc o insertaparenthesis; page 1;, secondoelend column, line 51 atter'a.

\um, line 71, Example 11;, for "e17" read oily; page 5, second colimn: for distillate (boiling! read distillate) boil ng,

read chlorine; pag B,

.5; and that the said'Lettere Patent therein tint the same may conform to 56, Example 19-, V 1 .7, same example, ror chloride" line I 7, claim 21, "or" 1.15"' read 1 should be read pith this correction LAWREICE H. FIE'IT.

195' to 300 C. and boiling for the most part irom 225' to 275 0., and containing about 5.8 per cent of unsaturated hydrocarbona'to produce a chlorination product containing mono-. diand poly-chlorinated hydrocarbons, condensing the resulting chlorination product with a phenol of the benzene series in the presence at zinc chloride as a condensing agent to form a mixture oi alkyl phenols and recovering a mixture of said alkyi phenols.

28. A process for the preparation of a mixture of alkyl cresols which comprises chlorinating a petroleum distillate consisting predominantly of saturated aliphatic hydrocarbons containing at least 12 carbon atoms to form mixed alkyl chlorides, condensing at least a portion of the resulting mixed alkyl chlorides with a cresol, and re covering a mixture of said alkyl cresols.

29. A process for the preparation of a mixture of higher alkyl cresols which comprises chlorinating a kerosene boiling from 195 to 300 C. and boiling for the most part from 225' to 2'15 0., and containing about 5.6 per cent of unsaturated hydrocarbons. to produce a chlorination product containing mono-, diand poly-chlorinated hydrocarbons. condensing the resulting chlorination product with a cresol in the presence of nnc chloride as a condensing agent. to form a mixture of higher aikyi cresols. and recovering a mixture Said h ther alkyl c'resols.

' LAWRENCE H. mm.

ilovemher 7, 1939.

in the printed specification tionas iollower Page 1, secline line

second column,

the record or the case in the Patent Office.

Signed and sealed this 6th Seal day of February,

Henry Van Lrsdale, acting Goaniasipneref ratents 

